Star-branched silicone polymers as anti-mist additives for coating applications

ABSTRACT

Star branched siloxane compounds suitable as anti-mist additives in the coating of flexible supports are made as the reaction product of: 
     
       
         M g ′M a M H   b−g D c D h ′D H   d−h T e T i ′T H   f−i  and (M j M Vi   k D l D Vi   m T n T Vi   o Q p ) q , 
       
     
     in the presence of a noble metal hydrosilylation catalyst where the ratio between the hydride containing precursor and the vinyl containing precursor is defined by a mathematical relationship between the stoichiometric subscripts of the precursors, (b+d+f−g−h−i)/(((k+m+o)p)q) ranging from 4.59 to 0.25 and where the compound: 
     
       
         M g ′M a M H   b−g D c D h ′D H   d−h T e T i ′T H   f−i   
       
     
     may be obtained by the following reaction: 
     
       
         M a M H   b D c D H   d T e T H   f +αCH 2 ═CHR 1 →M g ′M a M H   b−g D c D h ′D H   d−h T e T i ′T H   f−I , 
       
     
     which compound itself is a star branched siloxane compound useful as an anti-mist additive.

FIELD OF USE

The present invention relates to coating flexible materials or supportssuch as sheets of paper or other polymeric material, either woven ornon-woven, with a silicone composition. The present invention alsorelates to the coating of flexible materials or supports with liquidcompositions comprising one or more cross-linkable polyorganosiloxaneswherein such polyorganosiloxanes are cross-linkable by an additionreaction, a condensation reaction, a cationic reaction, or afree-radical reaction. The present invention also relates to starbranched polyorganosiloxanes (silicone polymers) that reduce mistingduring the application of the silicone composition (polyorganosiloxane)to the flexible material or support. The flexible support may be paper,cardboard, plastic film, metal film and the like. Some exemplaryapplications are paper for foodstuffs, adhesive labels, adhesive tapes,seals and the like.

BACKGROUND OF INVENTION

The coating of flexible supports with liquid silicones is typicallycarried out on coating devices that operate continuously at very highspeed. These devices usually comprise coating heads composed of severalrolls, including in particular a pressure roll and a coating roll thatare continuously fed with a silicone composition that may or may not becross-linkable, by means of a series of rolls that are placed next toone another. A strip of flexible support of the desired material to becoated is fed at high speed between the pressure roll and the coatingroll to be coated on at least one of its surfaces. When it is intendedto cross link the silicone coating, apparatus to implement a crosslinking reaction are positioned downstream of the coating head. Theapparatus that implements cross linking may be for example an oven or anemitter of radiation, e.g. ultraviolet (UV) radiation or an emitter of abeam of electrons (EB).

High speed coating of flexible supports with silicones has beenassociated with problems associated with the transfer of the siliconeliquid (or fluid) from the coating roll to the flexible support, whichmoves forward through the coating apparatus. One of the particularproblems associated with transfer of the silicone liquid from thecoating roll to the flexible support is the appearance of a fog, mist oraerosol in the immediate vicinity of the coating head and particularlyclose to the points of contact between the coating roll and the flexiblesupport being coated. Typically, the density of this fog, mist oraerosol increases with an increase in the forward speed of the flexiblesupport being coated by the apparatus.

The first effect of this transfer problem is to reduce the amount ofsilicone liquid actually transferred to the flexible support. A secondeffect is for the droplets comprising the fog, mist or aerosol tocondense onto the newly coated flexible support downstream of thecoating rolls creating an orange peel effect. This orange peel effect,or coating non-uniformity, creates problems with coverage, themechanical properties of the coating, e.g. ruboff, and adhesionresistance.

An additional problem caused by non-uniformity in the coating is relatedto industrial hygiene and the safety of people operating the coatingequipment who are working in the vicinity of the coating equipment.

BRIEF SUMMARY OF THE INVENTION

The present invention provides for a composition to reduce mistingduring the coating of flexible supports comprising the hydrosilylationreaction product of:

a) M_(a)M^(H) _(b)D_(c)D^(H) _(d)T_(e)T^(H) _(f); and

b) an amount α of CH₂═CHR¹

where α+1≦b+d+f and g≦b, h≦d, i≦f with 1.5≦b+d+f≦100;

2≦a+b≦12; 0≦c+d≦1000; 0≦e+f≦10 and R¹ is a monovalent radical selectedfrom the group consisting of halogens, hydrogen, C1 to C60 monovalenthydrocarbon radicals, C1 to C60 monovalent polyester radicals, C1 to C60monovalent nitrile radicals, C1 to C60 monovalent alkyl halide radicalsand C1 to C60 monovalent polyether radicals and mixtures thereof; where

M=R²R³R⁴SiO_(1/2);

M^(H)=HR⁵R⁶SiO_(1/2);

D=R⁷R⁸SiO_(2/2);

D^(H)=HR⁹SiO_(2/2);

T=R¹¹SiO_(3/2);

T^(H)=HSiO_(3/2);

and said reaction product has the formula:

M′=(CH₂CH₂R¹)R⁵R⁶SiO_(1/2);

 D′=(CH₂CH₂R¹)R⁹SiO_(2/2); and

T′=(CH₂CH₂R¹)SiO_(3/2)

with each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹¹ independently selectedfrom the group of C1 to C60 monovalent hydrocarbon radicals where thesubscripts a, b, c, d, e, f, g, h, and i are zero or positive subject tothe limitations that b+d+f−g−h−i>0.

The present invention further provides for a composition to reducemisting during the coating of flexible supports comprising thehydrosilylation reaction product of:

a) M_(g)′M_(a)M^(H) _(b−g)D_(c)D_(h)′D^(H) _(d−h)T_(e)T_(i)′T^(H) _(f−i)and

b) (M_(j)M^(Vi) _(k)D_(l)D^(Vi) _(m)T_(n)T^(Vi) _(o))_(p)Q_(p))_(q)where

the subscripts j, k, l, m, n, o and p are zero or positive subject tothe limitation that k+m+o>0, k+m+o<b+d+f−g−h−i, p ranges from 0.4 to4.0, q is non-zero and positive subject to the limitation that:

(b+d+f−g−h−i)/(((k+m+o)p)q) ranges from 4.59 to 0.25, where

M^(Vi)=R^(Vi)R⁵R⁶SiO_(1/2);

D^(Vi)=R^(Vi)R¹⁰SiO_(2/2);

T^(Vi)R^(Vi)SiO_(3/2);

Q=SiO_(4/2); where

R¹⁰ is independently selected from the group of C1 to C60 monovalenthydrocarbon radicals and each R^(Vi) is independently selected from thegroup of C2 to C60 monovalent alkenyl hydrocarbon radicals.

DETAILED DESCRIPTION OF THE INVENTION

The star branched siloxane compounds of the present invention are madeas the reaction product of:

M_(g)′M_(a)M^(H) _(b−g)D_(c)D_(h)′D^(H) _(d−h)T_(e)T_(i)′T^(H) _(f−i)and (M_(j)M^(Vi) _(k)D_(l)D^(Vi) _(m)T_(n)T^(Vi) _(o))_(p)Q_(p))_(q),

in the presence of a noble metal hydrosilylation catalyst where thesubscripts a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p, are zero orpositive and q is non-zero and positive, for mixtures of compounds theaverage values of each of the subscripts will most likely benon-integral, for specific compounds the subscripts will be integral,with k+m+o>0 and k+m+o<b+d+f−g−h−i, p ranges from 0.4 to 4.0, preferably0.5 to 3.0, more preferably 0.5 to 2.5 and most preferably 0.5 to 1.5and all sub-ranges there between and q ranges from 1 to 200, preferably1 to 100, more preferably 1 to 75 and most preferably 1 to 50 and allsub-ranges there between where the ratio between the hydride containingprecursor and the vinyl containing precursor is defined by the followingmathematical relationship between the stoichiometric subscripts of theprecursors, (b+d+f−g−h−i)/(((k+m+o)p)q) ranges from 4.59 to 0.25,preferably from 4.5 to 0.25; more preferably from 4.5 to 0.25 and mostpreferably from 4.0 to 0.25and all sub-ranges there between andspecifically including 3.5 to 0.25; 3.0 to 0.25; 2.5 to 0.25 and 2.0 to0.25; and where the compound:

M_(g)′M_(a)M^(H) _(b−g)D_(c)D_(h)′D^(H) _(d−h)T_(e)T_(i)′T^(H) _(f−i)

may be obtained by the following reaction:

M_(a)M^(H) _(b)D_(c)D^(H) _(d)T_(e)T^(H) _(f)+αCH₂═CHR¹→M_(g)′M_(a)M^(H)_(b−g)D_(c)D_(h)′D^(H) _(d−h)T_(e)T_(i)′T^(H) _(f−i)

where α+1≦b+d+f and g≦b, h≦d, i≦f with 1.5≦b+d+f≦100; 2≦a+b≦12;0≦c+d≦1000; 0≦e+f≦10 and R¹ is a monovalent radical selected from thegroup consisting of halogens, hydrogen, C1 to C60 monovalent hydrocarbonradicals, C1 to C60 monovalent polyester radicals, C1 to C60 monovalentnitrile radicals, C1 to C60 monovalent alkyl halide radicals and C1 toC60 monovalent polyether radicals and mixtures thereof; with

M=R²R³R⁴SiO_(1/2);

M^(H)=HR⁵R⁶SiO_(1/2);

M^(Vi)=R^(Vi)R⁵R⁶SiO_(1/2);

D=R⁷R⁸SiO_(2/2);

D^(H)=HR⁹SiO_(2/2);

D^(Vi)=R^(Vi)R¹⁰SiO_(2/2);

T=R¹¹SiO_(3/2);

T^(H)=HSiO_(3/2);

T^(Vi)=R^(Vi)SiO_(3/2);

Q=SiO_(4/2);

M′=(CH₂CHR¹)R⁵R⁶SiO_(1/2);

D′=(CH₂CHR¹)R⁹SiO_(2/2); and

T′=(CH₂CHR¹)SiO_(3/2)

with each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ independentlyselected from the group of C1 to C60 monovalent hydrocarbon radicals andeach R^(Vi) independently selected from the group of C2 to C60monovalent alkenyl hydrocarbon radicals; it should be noted that thecompositions of the present invention require b+d+f−g−h−i>0. Methods formaking MQ resins, such as (M_(j)M^(Vi) _(k)D_(l)D^(Vi) _(m)T_(n)T^(Vi)_(o))_(p)Q)_(q), are described in U.S. Pat. No. 5,817,729, U.S. Pat. No.5,399,614 and U.S. Pat. No. 2,676,182 herewith and hereby specificallyincorporated by reference. The phrase C1 to C60 is a carbon number rangeranging from 1 to 60 and includes both aliphatic and aromatic radicals,e.g. styryl, this range also includes the following specific sub-ranges,15 to 60, 30 to 60, 45 to 60, 1 to 15, 1 to 30, 1 to 45, 10 to 30, 10 to40, 10 to 50 and all sub-ranges therebetween.

The star branched silicone compounds of the present invention aredescribed as the reaction product of the following two compounds:

M_(g)′M_(a)M^(H) _(b−g)D_(c)D_(h)′D^(H) _(d−h)T_(e)T_(i)′T^(H) _(f−i)and ((M_(j)M^(Vi) _(k)D_(l)D^(Vi) _(m)T_(n)T^(Vi) _(o))_(p)Q)_(q),

because of the multiplicity of hydrosilylation sites available forreaction on each of the component molecules being reacted and thedifficulties of reducing such a stochastic chemical reaction to ananalytic description.

The compositions of the present invention may be made by neat reactionsor by reactions where the reactants are diluted by solvent. Because ofthe long chain nature of the substituents in these materials, neatreactions, i.e. reactions conducted in the absence of anynon-participating solvent, will tend to produce products that conform tothe molecular descriptions herein but possessing a more entangledmacro-structure. If less entangled macro-structures of these compoundsare desired, the preparative reactions should be conducted in suitablesolvent media, e.g. cyclic siloxanes, inert hydrocarbon solvents and thelike.

Many types of noble metal catalysts for this hydrosilylation reactionare known and such catalysts may be used for the reaction in the presentinstance. When optical clarity is required the preferred catalysts arecatalysts that are soluble in the reaction mixture. By noble metal,Applicants define Ru, Rh, Pd, Os, Ir, and Pt as noble metals and alsoinclude Ni in the definition because of its known hydrogenationactivity. Preferably the catalyst is a platinum compound and theplatinum compound can be selected from those having the formula(PtCl₂Olefin) and H(PtCl₃Olefin) as described in U.S. Pat. No.3,159,601, hereby incorporated by reference. The olefin shown in theprevious two formulas can be almost any type of olefin but is preferablyan alkenylene having from 2 to 8 carbon atoms, a cycloalkenylene havefrom 5 to 7 carbon atoms or styrene. Specific olefins utilizable in theabove formulas are ethylene, propylene, the various isomers of butylene,octylene, cyclopentene, cyclohexene, cycloheptene, and the like.

A further platinum containing material usable in the compositions of thepresent invention is the cyclopropane complex of platinum chloridedescribed in U.S. Pat. No. 3,159,662 hereby incorporated by reference.

Further the platinum containing material can be a complex formed fromchloroplatinic acid with up to 2 moles per gram of platinum of a memberselected from the class consisting of alcohols, ethers, aldehydes andmixtures of the above as described in U.S. Pat. No. 3,220,972 herebyincorporated by reference.

The catalyst preferred for use with liquid injection moldingcompositions are described in U.S. Pat. Nos. 3,715,334; 3,775,452; and3,814,730 to Karstedt. Additional background concerning the art may befound at J. L. Spier, “Homogeneous Catalysis of Hydrosilation byTransition Metals, in Advances in Organometallic Chemistry, volume 17,pages 407 through 447, F. G. A. Stone and R. West editors, published bythe Academic Press (New York, 1979). Persons skilled in the art caneasily determine an effective amount of platinum catalyst. Generally, aneffective amount for hydrosilylation ranges from about 0.1 to 50 partsper million of the total organopolysiloxane composition and allsub-ranges there between.

EXPERIMENTAL

By way of example, 19.9 grams (0.083 moles) of a C16-18 alpha olefin wasmixed under a blanket of nitrogen gas with 1000 grams (0.21 moles) of asilyl hydride terminated polydimethylsiloxane and 10 ppm Pt added asKarstedt catalyst. The reaction was heated and stirred at 95° C. forapproximately four hours to allow the olefin to add to the siloxanepolymer. Quantitative chemical analysis of residual SiH indicated thatthe desired amount of hydrogen had been consumed in attaching the olefinto the siloxane. Optionally this product may be isolated before furtherreaction.

5.2 grams (0.05 moles) of an ((M^(Vi))₂Q)₄ resin was added to theproduct of the first reaction. An additional 10 ppm Pt as Karstedtcatalyst was added and the reaction stirred and heated to 95° C. forapproximately four hours. Quantitative chemical analysis indicated thatthe vinyl and hydride functional groups had reacted to the desireddegree. This product was isolated and tested as an Anti Mist Additive asreported in Tables 1 and 2 below.

Table 1 shows examples of the synthesis of the structures of the antimist additives based on the path described above. The SiH/SiVinyl is theratio of moles of silyl hydrides available for reaction to the moles ofsilyl vinyl available for reaction. In the compounds shown, theSiH/SiVinyl ratio runs from 0.2 to 2.75, but a larger usable range spansfrom 0.22 to 4.5.

Table 2 shows the anti misting behavior of the invention. Themeasurements were made during runs on 2.5 mil SC Rhi-Liner 12 paperusing a pilot coater with a line speed of 2000 ft/minute. The paper wascoated with a standard silicone paper release formulation containing ˜2%anti mist additive with a target of 0.6 to 0.9 pounds per ream. The mistwas measured using a DustTrack Aerosol Monitor. The intake port waspositioned in the highest observed misting area thus providing thehighest expected values. The position does not reflect normalenvironmental testing nor does it guarantee specific values under alloperating conditions. The measurement is in mg of mist material percubic meter of air, the lower values being more desirable as theyrepresent less misting.

The results show the anti misting materials generated for this inventionreduce the amount of generated mist at 2000 ft/min compared to thecontrol formulation containing no anti mist additive. Quite surprisinglythe mist is often reduced by a factor of greater than ten, often byabout 100.

TABLE 1 Anti Mist Additive Synthesis Example Olefin Grams Silyl HydrideGrams ppm Pt SiH/SiVinyl gms ((Mvi)2Q)4 ppm Pt 20 C16-18 19.9 MHD125MH1000 10 2.50 5.2 10 21 C30+ 48.7 MHD125MH 1000 10 2.50 5.2 10 22 C16-1819.9 MHD125MH 1000 10 2.50 5.2 10 23 C16-18 37.2 MHD125MH 1500 10 2.008.1 10 24 C16-18 10.2 MHD125MH 500 5 1.20 5.2 5 25 C16-18 11.9 MHD125MH600 10 1.75 4.4 5 26 C16-18 11.9 MHD125MH 600 10 2.00 3.9 5 27 C16-184.0 MHD125MH 200 5 2.50 1.0 5

TABLE 2 Anti Mist Measurements AMA # Mg/m3 at 2000 ft/min control 102.00121B 20 34.60 346 21 10.00 347 22 1.60 370 23 1.73 122C 24 1.64 384 251.13 383 26 3.80 379A 27 0.43

The foregoing examples are merely illustrative of the invention, servingto illustrate only some of the features of the present invention. Theappended claims are intended to claim the invention as broadly as it hasbeen conceived and the examples herein presented are illustrative ofselected embodiments from a manifold of all possible embodiments.Accordingly it is Applicants' intention that the appended claims are notto be limited by the choice of examples utilized to illustrate featuresof the present invention. As used in the claims, the word “comprises”and its grammatical variants logically also subtend and include phrasesof varying and differing extent such as for example, but not limitedthereto, “consisting essentially of” and “consisting of.” Wherenecessary, ranges have been supplied, those ranges are inclusive of allsub-ranges there between. It is to be expected that variations in theseranges will suggest themselves to a practitioner having ordinary skillin the art and where not already dedicated to the public, thosevariations should where possible be construed to be covered by theappended claims. It is also anticipated that advances in science andtechnology will make equivalents and substitutions possible that are notnow contemplated by reason of the imprecision of language and thesevariations should also be construed where possible to be covered by theappended claims. All United States patents referenced herein areherewith and hereby specifically incorporated by reference.

What is claimed is:
 1. A composition to reduce misting during thecoating of flexible supports comprising the hydrosilylation product ofcomprising the hydrosilylation reaction product of: a) the reactionproduct of: i) M_(a)M^(H) _(b)D_(c)D^(H) _(d)T_(e)T^(H) _(f); and ii) anamount α of CH₂═CHR¹ where α+1<b+d+f with 1.5<b+d+f<100; 2<a+b<12;0<c+d<1000; 0<e+f≦10 and R¹ is a monovalent radical selected from thegroup consisting of halogens, hydrogen, C1 to C60 monovalent hydrocarbonradicals, C1 to C60 monovalent polyester radicals, C1 to C60 monovalentnitrile radicals, C1 to C60 monovalent alkyl halide radicals and C1 toC60 monovalent polyether radicals and mixtures thereof; whereM=R²R³R⁴SiO_(1/2); M^(H)=HR⁵R⁶SiO_(1/2); D=R⁷R⁸SiO_(2/2);D^(H)=HR⁹SiO_(2/2); T=R¹¹SiO_(3/2); T^(H)=HSiO_(3/2); and said reactionproduct has the formula: M_(g)′M_(a)M^(H) _(b−g)D_(c)D_(h)′D^(H)_(d−h)T_(e)T_(i)′T^(H) _(f−i) where M′=(CH₂CH₂R¹)R⁵R⁶SiO_(1/2);D′=(CH₂CH₂R¹)R⁹SiO_(2/2); and T′=(CH₂CH₂R¹)SiO_(3/2) with each R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹¹ independently selected from the group ofC1 to C60 monovalent hydrocarbon radicals where the subscripts a, b, c,d, e, f, g, h, and i are zero or positive subject to the limitation thatb+d+f−g−h−i>0 and b) (M_(j)M^(Vi) _(k)D_(l)D^(Vi) _(m)T_(n)T^(Vi)_(o))_(p)Q_(p))_(q) where the subscripts j, k, l, m, n, o and p are zeroor positive subject to the limitation that k+m+o>0, k+m+o<b+d+f−g−h−i, pranges from 0.4 to 4.0, q is non-zero and positive subject to thelimitation that: (b+d+f−g−h−i)/(((k+m+o)p)q) ranges from 4.59 to 0.25,where M^(Vi)=R^(Vi)R⁵R⁶SiO_(1/2); D^(Vi)=R^(Vi)R¹⁰SiO_(2/2);T^(Vi)=R^(Vi)SiO_(3/2); Q=SiO_(4/2); where R¹⁰ is independently selectedfrom the group of C1 to C60 monovalent hydrocarbon radicals and eachR^(Vi) is independently selected from the group of C2 to C60 monovalentalkenyl hydrocarbon radicals.
 2. The composition of claim 1 wherein R¹ ais selected from the group consisting of C1 to C60 monovalenthydrocarbon radicals, C1 to C60 monovalent polyester radicals, C1 to C60monovalent nitrile radicals, C1 to C60 monovalent alkyl halide radicalsand C1 to C60 monovalent polyether radicals.
 3. The composition of claim1 wherein R¹ a is selected from the group consisting of C15 to C60monovalent hydrocarbon radicals, C15 to C60 monovalent polyesterradicals, C15 to C60 monovalent nitrile radicals, C15 to C60 monovalentalkyl halide radicals and C15 to C60 monovalent polyether radicals. 4.The composition of claim 1 wherein R¹ a is selected from the groupconsisting of C30 to C60 monovalent hydrocarbon radicals, C30 to C60monovalent polyester radicals, C30 to C60 monovalent nitrile radicals,C30 to C60 monovalent alkyl halide radicals and C30 to C60 monovalentpolyether radicals.
 5. The composition of claim 2 where each R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are methyl.
 6. The composition of claim3 where each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are methyl. 7.The composition of claim 4 where each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, and R¹¹ are methyl.
 8. The composition of claim 1 wherein R¹ isstyryl.
 9. The composition of claim 8 where each R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, and R¹¹ are methyl.
 10. A composition comprising thehydrosilylation reaction product of: a) the reaction product of: j)M_(a)M^(H) _(b)D_(c)D^(H) _(d)T_(e)T^(H) _(f); and ii) an amount α ofCH₂═CHR¹ where α+1<b+d+f with 1.5<b+d+f<100; 2<a+b<12; 0<c+d<1000;0<e+f≦10 and R¹ is a monovalent radical selected from the groupconsisting of halogens, hydrogen, C1 to C60 monovalent hydrocarbonradicals, C1 to C60 monovalent polyester radicals, C1 to C60 monovalentnitrile radicals, C1 to C60 monovalent alkyl halide radicals and C1 toC60 monovalent polyether radicals and mixtures thereof; whereM=R²R³R⁴SiO_(1/2); M^(H)=HR⁵R⁶SiO_(1/2); D=R⁷R⁸SiO_(2/2);D^(H)=HR⁹SiO_(2/2); T=R¹¹SiO_(3/2); T^(H)=HSiO_(3/2); and said reactionproduct has the formula: M_(g)′M_(a)M^(H) _(b−g)D_(c)D_(h)′D^(H)_(d−h)T_(e)T_(i)′T^(H) _(f−i) where M′=(CH₂CH₂R¹)R⁵R⁶SiO_(1/2);D′=(CH₂CH₂R¹)R⁹SiO_(2/2); and T′=(CH₂CH₂R¹)SiO_(3/2) with each R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹¹ independently selected from the group ofC1 to C60 monovalent hydrocarbon radicals where the subscripts a, b, c,d, e, f, g, h, and i are zero or positive subject to the limitation thatb+d+f−g−h−i>0 and c) (M_(j)M^(Vi) _(k)D_(l)D^(Vi) _(m)T_(n)T^(Vi)_(o))_(p)Q_(p))_(q) where the subscripts j, k, l, m, n, o and p are zeroor positive subject to the limitation that k+m+o>0, k+m+o<b+d+f−g−h−i, pranges from 0.4 to 4.0, q is non-zero and positive subject to thelimitation that: (b+d+f−g−h−i)/(((k+m+o)p)q) ranges from 4.59 to 0.25,where M^(Vi)=R^(Vi)R⁵R⁶SiO_(1/2); D^(Vi)=R^(Vi)R¹⁰SiO_(2/2);T^(Vi)=R^(Vi)SiO_(3/2); Q=SiO_(4/2); where R¹⁰ is independently selectedfrom the group of C1 to C60 monovalent hydrocarbon radicals and eachR^(Vi) is independently selected from the group of C2 to C60 monovalentalkenyl hydrocarbon radicals.
 11. The composition of claim 10 wherein R¹a is selected from the group consisting of C1 to C60 monovalenthydrocarbon radicals, C1 to C60 monovalent polyester radicals, C1 to C60monovalent nitrile radicals, C1 to C60 monovalent alkyl halide radicalsand C1 to C60 monovalent polyether radicals.
 12. The composition ofclaim 10 wherein R¹ a is selected from the group consisting of C15 toC60 monovalent hydrocarbon radicals, C15 to C60 monovalent polyesterradicals, C15 to C60 monovalent nitrile radicals, C15 to C60 monovalentalkyl halide radicals and C15 to C60 monovalent polyether radicals. 13.The composition of claim 10 wherein R¹ a is selected from the groupconsisting of C30 to C60 monovalent hydrocarbon radicals, C30 to C60monovalent polyester radicals, C30 to C60 monovalent nitrile radicals,C30 to C60 monovalent alkyl halide radicals and C30 to C60 monovalentpolyether radicals.
 14. The composition of claim 11 where each R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are methyl.
 15. The composition ofclaim 12 where each R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ aremethyl.
 16. The composition of claim 13 where each R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are methyl.
 17. The composition of claim 10wherein R¹ is styryl.
 18. The composition of claim 17 where each R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are methyl.
 19. A process to reducemisting in the coating of a flexible substrate said process comprisingpreparing a coating composition for coating said substrate and addingthereto the composition of claim
 1. 20. A process to reduce misting inthe coating of a flexible substrate said process comprising preparing acoating composition for coating said substrate and adding thereto thecomposition of claim
 10. 21. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 11. 22. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 12. 23. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 13. 24. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 14. 25. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 15. 26. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 16. 27. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim
 17. 28. A process to reduce misting in the coatingof a flexible substrate said process comprising preparing a coatingcomposition for coating said substrate and adding thereto thecomposition of claim 18.